WO2014033622A2 - Conveniently prepared naphthalene and perylene derivatives as building blocks for organic electronic materials and dyestuff - Google Patents

Description

Conveniently prepared naphthalene and perylene derivatives as building blocks for organic electronic materials and dyestuff

Description

The invention relates to naphthalene and perylene derivatives.

Many naphthalene and perylene derivates are important colorants. Beside this traditional application, naphthalene and, in particular, perylene derivatives gain more and more interest in other applications such as in organic field-effect transistors, organic light emitting devices, photovoltaic devices such as dye-sensitized solar cells (DSCs), and xerography.

The design and preparation of naphthalene and perylene derivatives, which are tuned to be suitable for a particular application, are an active area of research.

Naphthalene and perylene derivatives, which are substituted in all four pen-positions, in particular with substituents such as cyano, alkyoxy, aryloxy, silyl, substituted amino, alkylthio, arylthio, alkyl and aryl, could be suitable for many applications.

DE 340091 describes the preparation of 3,4,9, 10-tetracyanoperylene from 3,4,9-tricyano-10- bromoperylene. 3,4,9-tricyano-10-bromoperylene was prepared from 3,4,9, 10-tetrabromo- perylene, which was obtained by bromination of perylene in nitrobenzene.

JP 2002-012861 describes perylene derivatives, which carry a substituted or unsubstituted amino group in the 1 or 2 position. In particular, JP 2002-012861 describes the preparation of 3,4,9, 10-tetraphenylperylene und 3,4,9, 10-tetracyanoperylene, both substituted in 1 and 7 position with a substituted amino group, from 1 ,7-dibromo-3, 4, 9, 10-tetraphenylperylene, respectively, 1 ,7-dibromoperylene 3,4,9, 10-tetracarbonitrile.

Zinke, A.; Pongratz, A., Funke, K. Chem. Ber. 1925, 58, 330 to 332 and DE 498 039 describes a process for the halogenation of perylene, wherein the halogenation is effected in the presence of a solvent such as nitrobenzene, and the halogen is employed in statu nascendi. According to the examples 3,9-dichloroperylene, tetrachloroperylene (mp. 350 °C), and hexachloroperylene (mp. 356 °C) are prepared by running an acetic acid solution of hydrogen peroxide into a solution of perylene in nitrobenzene at the same time as an acetic acid solution of concentrated hydrochloric acid is being added. It is said that the tetrachloroperylene is likely to be the 3,4,9,10- tetrachloroperylene. A further substitution of X is not described.

Many naphthalene derivatives, which are chlorinated or brominated in all four peri-positions, are known (DE 6661 1 , Whitehurst, J. S. J. Chem. Soc. 1951 , 221 to 226, Bassilios, H. F.; Salem, A. Y.; Shawky, M. Rec. Trav. Chim Pays-Bas 1962, 81, 209 to 214, DE 1958 595, Mesh, L. A.; Grudtsyn, Y.V. J. Org. Chem. USSR 1977, 13, 2384 to 2389, Brady, J. H.; Redhouse, A. D.; Wakefield, B. J. J. Chem. Res. Miniprint 'lQSl, 6, 1541 to 1554, Otsubo, T.; Sukenobe, N.; Aso, Y.; Ogura, F. Chem. Lett. 1987, 315 to 316, Garcia, R.; Riera, J.; Carilla, J.; Julia, L; Molins, E., Miravitlles C. J. Org. Chem. 1992, 57, 5712, Kodama, T.; Kodani, M.; Takimiya, K.; Aso, Y.; Otsubo, T. Heteroatom. Chem. 2001 , 12, 287 to 292).

DE 1 154 799 describes the following process

X = Br or CI

DE 1 154 799 emphasizes that it was not possible to obtain the tetrahalogenated naphthaline. A further substitution of X is not described.

It was the object of the present invention to provide naphthalene and perylene derivatives, which are substituted in all four pen-positions.

The object is solved by the process of claim 1 , the compounds of claim 8 and the compounds of claim 12.

The process of the present invention for the preparation of compounds of formula

wherein

n is 0 or 1 , R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰, Si(R³⁰¹ )3, NHR³⁰², NR³⁰³R³⁰⁴, SR³⁰⁵ and R³⁰⁶

wherein

R³⁰⁰, R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵ and R³⁰⁶ are d-20-alkyl, C₂-2o-alkenyl, C₂-₂o-alkynyl or wherein

Ci-20-alkyl, C2-2o-alkenyl and C2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O-R³⁰⁰² and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹¹ and R¹² together are selected from the group consisting of

0 ^0 _r 25 ^N ₂ ^N ^_{r 25} and s ^s

wherein

L¹ and L² are Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene,

R²⁵ is H, Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl, or C6-i4-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰¹⁰R³⁰¹¹, O-R³⁰¹² and S-R³⁰¹³, and

C6-i4-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR^{30 4}R³⁰¹⁵, O-R³⁰¹⁶ and S-R³⁰¹⁷,

wherein R³⁰¹⁰, R³⁰¹¹, R³⁰¹². R³⁰¹³, R³⁰¹⁴, R³⁰¹⁵, R³⁰¹⁶ and R³⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl,

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene, and

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, CI, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴,

wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are Ci-20-alkyl, C₂-2o-alkenyl, C₂-₂o-alkynyl,

Cs-s-cycloalkyl or Ce-14-aryl, wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

comprises the step of treating a compound of formula

wherein

n has the meaning as depicted for formula (3),

R⁹ and R¹⁰ are the same or different and are COOH or COOR²⁰⁰,

wherein R²⁰⁰ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰⁰⁰R²⁰⁰¹ ,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R²⁰⁰⁴R²⁰⁰⁵, O-R²⁰⁰⁶ and S-R²⁰⁰⁷, wherein R²⁰⁰⁰, R²⁰⁰¹ , R²⁰⁰² and R²⁰⁰³, R²⁰⁰⁴, R²⁰⁰⁵, R²⁰⁰⁶ and R²⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl

R⁹ and R¹⁰ together are

and

R¹ , R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, CI, Br, I, CN , R²⁰⁰, OR²⁰¹ , SR²⁰², OC(0)R²⁰³ and C(0)OR²⁰⁴,

wherein R²⁰⁰, R²⁰¹ , R²⁰², R²⁰³ and R²⁰⁴ are Ci-2o-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R^{201 1} , R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-io-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

a) with MOH, wherein M is an alkali metal, N(R⁴⁰⁰R⁴⁰ R⁴⁰²R⁴⁰³), P(R4oo_R4oi _R4o_2R403) _or

hexa(Ci-io-alkyl)guanidinium,

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰² and R⁴⁰³ are the same or different and are selected from the group consisting of H , Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl and C6-i4-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with phenyl,

Ce-14-aryl may be substituted with Ci-10-alkyl, and b) an X-donor, wherein X is CI, Br or I, in order to obtain a compound of formula

wherein

X has the meaning as depicted for the X-donor, n has the meaning as depicted for formula (3), and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the meaning as depicted for formula (2).

Ci-io-alkyl and Ci-20-alkyl can be branched or unbranched. Examples of Ci-10-alkyl are methyl, ethyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 1 ,1 -dimethyl- 3,3-dimethylbutyl, nonyl and decyl. Examples of Ci-20-alkyl are Ci-10-alkyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl,

C2-2o-alkenyl can be branched or unbranched. Examples of C2-2o-alkenyl are vinyl, propenyl, cis-

2- butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, trans-

3- pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl, linoleyl (ds), linolenyl (Cis), oleyl (Cis) and arachidonyl (C20).

C2-2o-alkynyl can be branched or unbranched. Examples of C2-2o-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptade- cynyl, octadecynyl, nonadecynyl and icosynyl (C20). Examples of Cs-s-cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Examples of Ce-14-aryl are phenyl and naphthyl.

Examples of halogen are F, CI, Br and I .

Examples of alkali metals are Na, K and Li.

Examples of N(R⁴⁰⁰R⁴⁰¹ R⁴⁰²R⁴⁰³) are tetra (n-butyl)ammonium and decyl-methyl-dioctyl- ammonium.

Examples of hexa(Ci-io-alkyl)-guanidinium are hexamethylguanidinium and

hexaethylguanidinium.

Examples of X-donors are X-X, X-succinimide and N ,N ^'-di-X-isocyanuric acid.

Preferably, R^{1 1} and R¹² are the same and are selected from the group consisting of CN , OR³⁰⁰ and Si(R³⁰¹)₃,

wherein

R³⁰⁰ and R³⁰¹ are Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl or C6-i4-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl and C2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰⁰⁰R³⁰⁰¹ , O-R³⁰⁰² and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or and R¹² together are

wherein

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene. More preferably, R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

wherein

_R3oo _{and R}3oi _are c_1-20-alkyl or C₆-i4-aryl,

wherein

Ci-2o-alkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰⁰⁰R³⁰⁰¹ , O-R³⁰⁰² and S-R³⁰⁰³ and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹¹ and R¹² together are

Most preferably, R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

wherein

_R3oo _{and R}3oi _are c_1-20-alkyl or C₆-i4-aryl,

wherein

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are

Ci-io-alkyl or phenyl, or

R¹¹ and R¹² together are

Preferably, n is 1 ,

Preferably, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, CI, Br, I, CN and OR³¹¹ ,

wherein R³¹¹ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl,

wherein Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

AA

Preferably, if n is 0, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are H.

Preferably, if n is 1 , R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰, are the same or different and are selected from the group consisting of F, CI, Br, I , CN , R³¹⁰, OR^{31 1} , SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴,

wherein R³¹⁰, R^{31 1} , R³¹², R³¹³ and R³¹⁴ are Ci-20-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl,

Cs-s-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

AA or _

More preferably, if n is 1 , R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰ are the same or different and are selected from the group consisting of CI, Br, I , CN and OR³¹¹,

wherein R³¹¹ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl, wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

Most preferably, if n is 1 , R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰ are the same or different and are selected from the group consisting of CI, Br, I and CN .

Even most preferably, if n is 1 , R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰ are CI.

Preferably, R⁹ and R¹⁰ are the same and are COOH , or

R⁹ and R¹⁰ together are

More preferably, R⁹ and R¹⁰ together are

Preferably, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, CI, Br, I , CN and OR²⁰¹,

wherein R²⁰¹ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl,

wherein Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R^{201 1} , R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

AA

Preferably, if n is 0, R¹, R², R³ and R⁴ are H.

Preferably, if n = 1 , R¹ , R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶, are the same or different and are selected from the group consisting of F, CI, Br, I , CN , R²⁰⁰, OR²⁰¹ , SR²⁰², OC(0)R²⁰³, and C(0)OR²⁰⁴,

wherein R²⁰⁰, R²⁰¹ , R²⁰², R²⁰³ and R²⁰⁴ are Ci-20-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R^{201 1} , R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

More preferably, if n is 1 , R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same or different and are selected from the group consisting of CI , Br, I , CN and OR²⁰¹,

wherein R²⁰¹ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl, wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰¹⁰R²⁰¹¹, O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

Most preferably, if n is 1 , R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same or different and are selected from the group consisting of CI, Br and OR²⁰¹,

wherein R²⁰¹ is C6-i4-aryl,

wherein

Ce-14-aryl may be substituted with Ci-10-alkyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

Preferably, M is an alkali metal, more preferably Na. Preferably, X is CI or Br, more preferably Br.

Preferably, the compound of formula (2) is first treated with MOH, followed by treatment with the X-donor. Usually the process is performed without the isolation of any intermediate products in a so-called "one pot reaction".

The compound of formula (2) is commercially available or can be obtained by methods known in the art. Preferably, the X-donor is X-X. More preferably, the X-donor is X-X, wherein X is CI or Br. Most preferably, the X-donor is X-X, wherein X is Br.

Preferably, the treatment with MOH and the treatment with the X-donor are performed in an aqueous solvent such as water or mixtures of water with a suitable organic solvent such as tet- rahydrofuran or dioxane. More preferably, the treatment with MOH and the treatment with the X-donor are performed in water as solvent.

Preferably, the treatment with MOH is performed at a temperature from 10 to 100 °C, more preferably from 20 to 60 °C.

Preferably, the molar ratio of MOH/compound of general formula (2) is 4/1 to 20/1 , more preferably 4/1 to 10/1 , most preferably 4/1 to 7/1 .

Preferably, the molar ratio of the X-donor/compound of general formula (2) is 4/1 to 30/1 , more preferably 4/1 to 20/1 , most preferably 4/1 to 17/1.

Preferably, the treatment with the X-donor is performed at a temperature from 10 to 260 °C, more preferably from 20 to 120 °C, most preferably from 20 to 100 °C.

The compound of formula (1 ) can be isolated by methods known in the art, for example by extraction with a suitable organic solvent such as dichloromethane. After isolation the compound of formula (1 ) may be further purified by methods known in the art, such as recrystallization or chromatography.

The compounds of formula (3) can be directly obtained from the compounds of formula (1 ) or via intermediate compounds in a multiple steps by methods known in the art.

For example, the compounds of formula (3), wherein R¹¹ and R¹² are both CN or OR³⁰⁰, can be prepared by treating the compound of formula (1 ) with M²CN or M²OR³⁰⁰, wherein M² can be an alkali metal or a transition metal.

For example, the compounds of formula (3), wherein R¹¹ and R¹² both are Si(R³⁰¹)3, can be prepared by treating the compound of formula (1 ) with an organyl-M³, wherein M³ can be an alkali metal, followed by X²-Si(R³⁰¹)3, wherein X² can be halogen.

For example, the compounds of formula (3), wherein R¹¹ and R¹² together are

can be prepared by treating the compound of formula (1 ) with sulphur. For example, the compounds of formula (3), wherein R¹¹ and R¹² both are NHR³⁰², NR³⁰³R³⁰⁴, respectively, SR³⁰⁵ can be prepared by treating the compound of formula (1 ) with NH2R³⁰², NHR³⁰³R³⁰⁴, respectively, HSR³⁰⁵.

For example, the compounds of formula (3), wherein R¹¹ and R¹² both are R³⁰⁶ can be prepared by treating the compound of formula (1 ) with R³⁰⁶boronic acid in the presence of a suitable catalyst such as Pd[P(Ph)₃]₄.

For example, the compounds of formula

(3a) can be prepared by treating the compound of formula

(1 b) with sulfur. For example the compound of formula

For example, the compound of formula

(3c) be prepared by treating the compound of formula

(1 b) with n-butyl lithium and trimethylsilyl chloride.

For example, the compound of formula

(3d) can be prepared by treating a compound of formula

(1 b) with CuCN.

Also part of the present invention are compounds of formula

wherein

X is CI, Br or I, n is 0 or 1 , and

R¹ , R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, CI, Br, I, CN , R²⁰⁰, OR²⁰¹ , SR²⁰², OC(0)R²⁰³ and C(0)OR²⁰⁴,

wherein R²⁰⁰, R²⁰¹ , R²⁰², R²⁰³ and R²⁰⁴ are Ci-₂₀-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen, Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

with the proviso

that if n is 0 and X is CI, R¹, R², R³ and R⁴ are not H, CI, CN, R²⁰⁰ or C(0)OR²⁰⁴,

wherein R²⁰⁰ and R²⁰⁴ are Ci-2o-alkyl,

that if n is 0 and X is Br, R¹, R², R³ and R⁴ are not H, Br or R²⁰⁰,

wherein R²⁰⁰ is Ci-20-alkyl, and

that if n is 1 and X is CI or br, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are not H.

Preferred are compounds of formula

wherein

X is CI, Br or I, n is 1 , and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, CI, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(0)R²⁰³ and C(0)OR²⁰⁴, wherein R²⁰⁰, R²⁰¹ , R²⁰², R²⁰³ and R²⁰⁴ are Ci-20-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen, wherein R²⁰¹⁰, R^{201 1} , R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl

or

R³ and R⁵, respectively, R⁴ and R⁶ together are

with the proviso

that if n is 1 and X is CI or Br, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are not H.

More preferred are compounds of formula

wherein

X is CI, Br or I, n is 1 , and R¹ , R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶, are the same or different and are selected from the group consisting of F, CI, Br, I, CN , R²⁰⁰, OR²⁰¹ , SR²⁰², OC(0)R²⁰³ and C(0)OR²⁰⁴,

wherein R²⁰⁰, R²⁰¹ , R²⁰², R²⁰³ and R²⁰⁴ are Ci-2o-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R^{201 1} , R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-io-alkyl or phenyl,

R³ and R⁵, respectively, R⁴ and R⁶ together are

The preferences of n, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and X given above for the process for the preparation of compounds of formula (3), also apply to the compounds of formula (1).

In particular preferred are the following compounds

Also part of the present invention are compounds of formula

wherein

n is 0 or 1 ,

R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰, Si(R³⁰¹)3, NHR³⁰², NR³⁰³R³⁰⁴, SR³⁰⁵ and R³⁰⁶

wherein

R³⁰⁰, R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵ and R³⁰⁶ are Ci_-2o-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl or wherein

Ci-2o-alkyl, C_2-2o-alkenyl and C_2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O-R³⁰⁰² and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹¹ and R¹² together are selected from the group consisting of wherein

L¹ and L² are Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene, R²⁵ is H, Ci-2o-alkyl, C_2-2o-alkenyl, C_2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl,

wherein Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰¹⁰R^{301 1} , O-R³⁰¹² and S-R³⁰¹³, and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{30 4}R³⁰¹⁵, O-R³⁰¹⁶ and S-R³⁰¹⁷,

wherein R³⁰¹⁰, R^{301 1} , R³⁰¹². R³⁰¹³, R³⁰¹⁴, R³⁰¹⁵, R³⁰¹⁶ and R³⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl,

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene, and

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, CI, Br, I , CN , R³¹⁰, OR^{31 1} , SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴,

wherein R³¹⁰, R^{31 1} , R³¹², R³¹³ and R³¹⁴ are Ci-20-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl,

Cs-s-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

J with the proviso that if

n is 0, R^{1 1} and R¹² are both CN , then R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are not all H,

and that if

n is 1 , R^{1 1} and R¹² are both CN or phenyl, and R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are H, then R¹⁷ and R²⁰ are not Br. Preferred are the compounds of formula

wherein

n is 0 or 1 ,

R^{1 1} and R¹² are the same and are selected from the group consisting of CN , OR³⁰⁰ and

Si(R³⁰¹)₃,

wherein

R³⁰⁰ and R³⁰¹ are Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl and C2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰⁰⁰R³⁰⁰¹ , O-R³⁰⁰² and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R^{1 1} and R¹² together are

wherein

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene, and R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, CI, Br, I, CN , R³¹⁰, OR^{31 1} , SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴,

wherein R³¹⁰, R^{31 1} , R³¹², R³¹³ and R³¹⁴ are Ci-20-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

with the proviso

that if n is 0, R¹¹ and R¹² are both CN, then R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are not all H,

and

that if n is 1 , R¹¹ and R¹² are both CN or phenyl, and R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are H, then R¹⁷ and R²⁰ are not Br.

More preferred are compounds of formula

wherein

n is 1 ,

R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and

Si(R³⁰ )₃,

wherein

R³⁰⁰ and R³⁰¹ are Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl or C6-i4-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl and C2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O-R³⁰⁰² and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹¹ and R¹² together are

^S ^_L3 .^S wherein

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene, and

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, CI, Br, I , CN , R³¹⁰, OR^{31 1} , SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴,

wherein R³¹⁰, R^{31 1} , R³¹², R³¹³ and R³¹⁴ are Ci-2o-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen, wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

with the proviso

that if n is 1 , R¹¹ and R¹² are both CN or phenyl, and R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are H, then R¹⁷ and R²⁰ are not Br.

Even more preferred are compounds of formula

wherein

n is 1 ,

R^{1 1} and R¹² are the same and are selected from the group consisting of CN , OR³⁰⁰ and Si(R³⁰ )₃,

wherein

R³⁰⁰ and R³⁰¹ are Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl and C2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰⁰⁰R³⁰⁰¹ , O-R³⁰⁰² and S-R³⁰⁰³ and

C6-i4-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or and R¹² together are

^S ^_L3 ^^S wherein

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene, and

R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰, are the same or different and are selected from the group consisting of F, CI, Br, I, CN , R³¹⁰, OR^{31 1} , SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴, wherein R³¹⁰, R^{31 1} , R³¹², R³¹³ and R³¹⁴ are Ci-20-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

Most preferred are compounds of formula

wherein

n is 1 ,

R^{1 1} and R¹² together are

R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰, are the same or different and are selected from the group consisting of F, CI , Br, I, CN , R³¹⁰, OR^{31 1} , SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴, wherein R³¹⁰, R^{31 1} , R³¹², R³¹³ and R³¹⁴ are d-20-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl,

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

(3c) and

(3d)

The compounds of formula (3) can be used in various applications, for example as colorants or dyes, or in electronic devices such in organic field-effect transistors, organic light emitting devices and in photovoltaic devices such as dye-sensitized solar cells (DSCs).

Also part of the invention is the use of the compounds of formula (3) in electronic devices.

Also part of the invention is the use of the compounds of formula (3) as dye.

The process of the present invention is advantageous as it allows the convenient preparation of compounds of formula (3).

The key intermediates of the process of the present invention for the preparation of the compounds of formula (3) are the compounds of formula (1 ) carrying four X-groups, wherein X is CI, Br or I, in the per/^'-positions. The compounds of formula (1 ) are versatile building blocks, which allow the easy introduction of various substituents in the pen-positions by methods known in the art. In case, the compounds of formula (1 ) also carry suitable substituents such as CI in the R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and/or R⁸ positions, these substituents can also be easily replaced with other substituents. The compounds of formula (1 ) can be prepared in a very convenient and economic manner from the compounds of formula (2) The compounds of formula (2), especially the compounds of formula (2), wherein R⁹ and R¹⁰ together are

are readily available and of low cost. The compounds of formula (1 ) are usually obtained in high yields (for example higher than 80%), especially when n is 1 , X is Br, and R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same and are selected from the group consisting of H, CI, and Br, or R³ and R⁵, respectively, R⁴ and R⁶ together are

AA

Steps a) and b) can be performed at moderate temperatures, for example at temperatures below 100 °C. In addition, the steps a) and b) can be performed in an aqueous solvent such as water, and in a so-called "one pot reaction".

Examples Example 1

Preparation of compound 1a

20 ml 1 M NaOH was added to a suspension of compound 2a (4.00 mmol) in 20 ml water and the mixture was stirred to obtain a limpid solution. Bromine (1 .0 ml, 3.1 1 g) was added in one portion and the reaction mixture was stirred at 90-95 °C for 24 h. The precipitate was filtered and dried. The crude solid was extracted with dichloromethane. Organic solvent was evaporated to dryness and compound 1a was purified by column chromatography using hexane as eluent on silica. Yield 180 mg (10%). FD-Mass: calc: 443.75 found: 444.0. ¹H-NMR (δ (ppm), CD2CI2): 7.66 (s, 4H, CH); ³C-NMR (δ (ppm), CD2CI2): 120.54 (4C, CBr); 130.49 (2C, C);

135.91 (4C, CH).

Example 2

Preparation of compou

(2b) (1 b)

10 ml 1 M NaOH was added to a suspension of compound 2b (2.00 mmol) in 20 ml water and the mixture was stirred at 55 °C for 30 min. Bromine (1.0 ml) was added and reaction mixture was stirred for 24 h. The precipitate was filtered and dried. Crude compound 1 b was purified by sublimation (1.27 g; 90%) or recrystallization from 1 ,2-dichlorobenzene (1.17 g; 83%). FD-Mass: calc: 705.67 found: 706.0. MALDI-TOF: calc: 705.67 found: 705.75. Elemental analysis: calc: % C 34.04; % H 0.57; found: % C 34.23; % H 0.70. H-NMR (δ (ppm), 1 ,2-dichlorobenzene-d₄): 7.80 (s, 4H).

Example 3

Preparation of compound 1 c

(2c) (1c) 10 ml 1 M NaOH was added to a suspension of compound 2c (1.42 g, 2.00 mmol) in 30 ml water and the mixture was stirred at 55 °C for 30 min. Bromine (1.0 ml) was added and reaction mixture was stirred for 24 h. The precipitate was filtered and dried (1.70 g, 96%). The crude compound 1c was purified by recrystallization from 1 ,2-dichlorobenzene (1 .47 g; 83%). FD-Mass: calc: 883.48 found: 883.7. Elemental analysis: calc: % C 27.19; % H 0.46; found: % C 27.34; % H 0.53. H-NMR (δ (ppm), 1 ,2-dichlorobenzene-d₄): 7.96 (s, 4H).

Example 4

Preparation of compound 1d

(1d)

After adding 3 ml 1 M NaOH to a solution of compound 2d (0.50 mmol) in 10 ml water THF was added to obtain a clear solution. Bromine (0.40 ml) was added in one portion and the reaction mixture was stirred at room temperature for 0.5 to 1 h (TLC monitoring). A Solution of Na2S03 (1 g in 10 ml water) was added and stirred for 20 min. Compound 1d was extracted with di- chloromethane and purified by column chromatography using hexane as eluent on silica. Yield 5-30 mg (1 -6%). H-NMR (δ (ppm), CD₂CI₂): 0.67 (s, 36H, CH₃); 1.27 (s, 12H, CH₃); 1.28 (s, 12H, CH₃); 1 .65 (s, 8H, CH₂); 6.72 (d, 8H, ³J_HH = 8.7 Hz); 7.19 (d, 8H, ³J_HH = 8.7 Hz); 7.32 (s, 4H). FD-Mass: calc: 1385.13; found: 1385.9.

Example 5

Preparation of compound 2e

(2b) (2e)

1 M NaOH (22 ml) was added to a mixture of compound 2b (2.65 g, 5.00 mmol) and 18 ml water under argon. The mixture was stirred at 70 °C for 30 min and 1 ml Aliquat 336 (Stark' catalyst) was added and stirred additional 10 min at the same temperature. 1 -lodoheptane was added and the reaction mixture was refluxed for 2 h. After cooling down to room temperature, the mixture was extracted with dichloromethane. The solvent was removed under vacuum and crude compound 2e was purified by column chromatography (silica gel, petroleum ether/

dichloromethane). Yield 4.315 g (90%) as orange oil. FD-Mass: calc: 958.87; found: 959.7. H-NMR (δ (ppm), CDCI₃): 0.82 (t, 12H, CH₃, ³JHH = 6.7 Hz); 1 .18-1 .43 (m, 32H, CH₂); 1 .74 (p, 8H, ³JHH = 6.9 Hz, CH₂); 4.21 -4.34 (m, 8H, CH₂0); 8.01 (s, 4H, CH-perylene). ³C-NMR (δ (ppm), CDCIs): 14.20 (4C, CH₃); 22.73 (4C, CH₂); 26.06 (4C, CH₂); 28.66 (4C, CH₂); 29.1 1 (4C, CH₂); 31 .84 (4C, CH₂); 66.48 (4C, CH₂0); 123.24 (2C); 127.32 (4C); 130.90 (4C); 132.12 (4C); 133.67 (4C); 134.06 (2C); 167.1 1 (4C, CO). Elemental analysis calcd (%) for C₅₂H₆4Cl40₈: C 65.13, H 6.73; found: C 65.17, H 6.87.

Example 6

Preparation of compound 2f

Pd(PPh₃)₄ (780 mg, 0.67 mmol) and Bu₃SnSSnBu₃ (3.67 g, 6.00 mmol) were added to a solution of compound 2e (2.60 g, 2.71 mmol) in 100 ml toluene under argon. The mixture was stirred and refluxed for 24 h. The solvent was removed under vacuum and the crude compound 2f was washed with methanol and purified by column chromatography (silica gel, petroleum ether/ethyl acetate). Yield 1 .58 g (66%). H-NMR (δ (ppm), CDCI₃): 0.83 (t, 12H, CH₃, ³J_HH = 6.9 Hz); 1.26-1.48 (m, 32H, CH₂); 1 .83 (p, 8H, ³J_HH = 6.9 Hz, CH₂); 4.42 (t, 8H, CH₂0, ³JHH = 6.9 Hz); 8.74 (s, 4H, CH-perylene). ³C-NMR (δ (ppm), CDCI₃): 14.22 (4C, CH₃); 22.78 (4C, CH₂); 26.26 (4C, CH₂); 28.91 (4C, CH₂); 29.24 (4C, CH₂); 31.92 (4C, CH₂); 66.22 (4C, CH₂0); 120.98 (2C); 121 .54 (2C); 125.31 (4C); 129.60 (4C); 131 .13 (4C); 136.83 (4C); 168.61 (4C, CO).

Elemental analysis calcd (%) for C52H64O8S2: C 70.88, H 7.32; S 7.28 found: C 70.85, H 76.48, S 7.22.

Example 7

Preparation of compound 2g

KOH (2.25 g, 34 mmol) and 5 ml water were added to a solution of compound 2f (1 .5 g, 1.70 mmol) in 100 ml 2-propanol. The reaction mixture was refluxed overnight. After cooling the reaction mixture was poured onto ice/10% hydrochloric acid. The precipitate was filtered, washed with water and methanol and dried. The solid was suspended in acetic acid (50 ml) and stirred at 70 °C for 5 h. The acetic acid was removed under vacuum. The crude compound 2g was used without further purification. Yield 0.75 g (98%). FD-Mass: calc: 452.41 ; found: 453.2

4.5 ml 1 M NaOH was added to a suspension of compound 2g (0.455 g, 1.00 mmol) in 20 ml water and the mixture was stirred at 30 °C for 20 min. Bromine (0.21 ml, 4.1 mmol) was added and the reaction mixture was stirred for 10 min at 30 °C. The precipitate was filtered, washed with water and dried. The crude compound 1e was suspended in THF (20 ml) and filtered, washed and dried (0.56 g; 89%). MALDI-TOF: calc: 627.99 found: 627.8 Elemental analysis calcd (%) for C2oH₄Br₄S2: C 38.25, H 0.64; S 10.21 found: C 37.95, H 1 .39, S 9.65.

Example 9

Preparation of compound 3a

(1 b) (3a)

A suspension of 3,4,9, 10-tetrabromo-1 ,6,7,12-tetrachloroperylene (0.71 g, 1.00 mmol) and sulfur (0.26 g, 8.0 mmol) in 40 ml NMP was stirred at 190 °C for 3 h. After cooling down to room temperature the reaction mixture was poured into water. The precipitate was filtered, washed with water and dried. The crude compound 3a was purified by column chromatography using dichloromethane as eluent on silica (0.50 g, 97%). FD-Mass: calc: 514.32; found: 514.1. ¹H- NMR (δ (ppm), DMSO-d₆): 7.72 (s, 4H).

A mixture of compound 1 b (706 mg, 1 mmol), 4-(2,4,4-trimethylpentan-2-yl)phenol (1240 mg, 6 mmol) and K₂C0₃ (830 mg, 6 mmol) in 30 ml NMP was stirred at 120 °C for 5 h. The mixture was cooled down to room temperature and dichloromethane (100 ml) was added. The solution was washed several times with water, dried and evaporated. Crude compound 3b was purified by column chromatography using hexane/dichloromethane as eluent on silica. Yield 890 mg (74%). H-NMR (δ (ppm), CD₂CI₂): 0.66 (s, 36H, CH₃); 1 .27 (s, 24H, CH₃); 1.65 (s, 8H, CH₂); 6.72 (d, 8H, ³JHH = 8.7 Hz); 6.88 (s, 4H); 7.24 (d, 8H, ³J_HH = 8.8 Hz). ³C-NMR (δ (ppm), CD₂CI₂): 31 .98 (4C, CH₃); 32.01 (4C, CH₃); 32.15 (12C, CH₃); 32.83 (4C, CH₂); 38.77 (4C); 57.47 (4C); 1 16.29 (2C); 1 17.98 (4C); 1 18.61 (8C, CH); 121 .30 (4C); 128.20 (8C, CH); 133.66 (4C); 137.32 (2C); 146.44 (4C, CH); 154.01 (4C); 154.98 (4C). FD-Mass: calc: 1207.32; found: 1208.1 .

Example 1 1

Preparation of compound 3c

(1 b) (3c)

4.40 ml of solution of n-BuLi (1 .6 M, 7 mmol) was added to a suspension of compound 1 b

(1 mmol, 706 mg) in 20 ml dry THF at -78°C. The reaction mixture was stirred at -78 °C for 1 h and TMSCI (0.90 ml, 7 mmol) was added dropwise to the solution. The mixture was allowed to warm gradually to room temperature and stirred additional 2 h. Methanol (1 ml) was added and the solvents were evaporated. The crude compound 3c was purified by column chromatography using hexane as eluent on silica and additional recrystallization from methanol. Yield 325 mg (48%). H-NMR (δ (ppm), CDCI₃): 0.52 (s, 18H, CH₃); 0.54 (s, 18H, CH₃); 7.68 (s, 2H); 8.18 (s, 2H). ³C-NMR (δ (ppm), CD₂CI₂): 0.07 (6C, CH₃); 0.28 (6C, CH₃); 125.59 (2C); 125.84 (2C); 131.39 (2C); 132.67 (2C); 134.52 (2C); 134.93 (2C); 135.58 (2C); 138.28 (2C); 138.76 (2C); 140.26 (2C).

Example 12

Preparation of compound 3d

Ob) (3d)

A suspension of compound 1 b (2.1 1 g, 3.00 mmol) and CuCN (5.40 g, 60 mmol) in 50 ml DMF was stirred at 130 °C for 2 h. After cooling down to room temperature the reaction mixture was poured in water. The precipitate was filtered, dried and dissolved in 600 ml dichloromethane. 20 g of silica was added to the solution and evaporated to dry- ness. Crude compound 3d was purified by column chromatography using dichloro- methane as eluent on silica. (1.03 g, 70%). FD-Mass: calc: 490.13; found: 489.7. ¹H-NMR (δ (ppm), C₂D₂CI₄): 8.21 (s, 4H, CH).

Claims

Claims

1 . A process for the preparation of compounds of formula

wherein

n is 0 or 1 ,

R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰,

Si(R³⁰¹)₃, NHR³⁰², NR³⁰³R³⁰⁴, SR³⁰⁵ and R³⁰⁶,

wherein

R³⁰⁰, R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵ and R³⁰⁶ are Ci-₂₀-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl or wherein

Ci-2o-alkyl, C_2-2o-alkenyl and C_2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O-R³⁰⁰² and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹¹ and R¹² together are selected from the group consisting of

wherein

L¹ and L² are Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene,

PF 74208 UGA [ggf. Fig/Seq] R²⁵ is H, Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰¹⁰R³⁰¹¹, O-R³⁰¹² and S-R³⁰¹³, and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR^{30 4}R³⁰¹⁵, O-R³⁰¹⁶ and S-R³⁰¹⁷,

wherein R³⁰¹⁰, R³⁰¹¹, R³⁰¹². R³⁰¹³, R³⁰¹⁴, R³⁰¹⁵, R³⁰¹⁶ and R³⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl,

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene, and

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H , F, CI, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴, wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are Ci-2o-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

Cs-s-cycloalkyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰²⁰R³⁰²¹, O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

which process comprises the step of treating a compound of formula

wherein

n has the meaning as depicted for formula (3),

R⁹ and R¹⁰ are the same or different and are COOH or COOR²⁰⁰,

wherein R²⁰⁰ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰⁰⁰R²⁰⁰¹ ,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R²⁰⁰⁴R²⁰⁰⁵, O-R²⁰⁰⁶ and S-R²⁰⁰⁷,

wherein R²⁰⁰⁰, R²⁰⁰¹ , R²⁰⁰² and R²⁰⁰³, R²⁰⁰⁴, R²⁰⁰⁵, R²⁰⁰⁶ and R²⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R⁹ and R¹⁰ together are

and

R¹ , R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, CI, Br, I , CN , R²⁰⁰, OR²⁰¹ , SR²⁰², OC(0)R²⁰³ and C(0)OR²⁰⁴, wherein R²⁰⁰, R²⁰¹ , R²⁰², R²⁰³ and R²⁰⁴ are Ci-₂₀-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl,

Cs-s-cycloalkyl or Ce-14-aryl,

wherein Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R^{201 1} , R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

a) with MOH, wherein M is an alkali metal, N(R⁴⁰⁰R⁴⁰ R⁴⁰²R⁴⁰³), P(R4oo_R4oi _R4o_2R403) _or hexa(Ci-io-alkyl)guanidinium,

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰² and R⁴⁰³ are the same or different and are selected from the group consisting of H , Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl and C6-i4-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with phenyl,

Ce-14-aryl may be substituted with Ci-10-alkyl, and b) an X-donor, wherein X is CI, Br or I , in order to obtain a compound of formula

wherein

X has the meaning as depicted for the X-donor, n has the meaning as depicted for formula (3), and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the meaning as depicted for formula (2). The process of claim 1 , wherein R⁹ and R¹⁰ together are

The process of claim 1 or claim 2, wherein n is 1.

The process of any of claims 1 to 3, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, CI, Br, I, CN and OR²⁰¹ wherein R²⁰¹ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰¹⁰R²⁰¹¹, O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

The process of any of claims 1 to 4, wherein R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, CI, Br, I, CN and OR³¹¹,

wherein R³¹¹ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl, wherein Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S- R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen,

wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

The process of any of claims 1 to 5, wherein R^{1 1} and R¹² are the same and are selected from the group consisting of CN , OR³⁰⁰ and Si(R³⁰¹)₃,

wherein

R³⁰⁰ and R³⁰¹ are Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl or C6-i4-aryl,

wherein

Ci-20-alkyl, C2-2o-alkenyl and C2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰⁰⁰R³⁰⁰¹ , O-R³⁰⁰² and S-R³⁰⁰³ and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R^{1 1} and R¹² together are

^S^_L3.^S wherein

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene.

The process of any of claims 1 to 6, wherein R^{1 1} and R¹² are the same and are selected from the group consisting of CN , OR³⁰⁰ and Si(R³⁰¹)₃,

wherein

_R3oo _{and R}3oi _are c_1-20-alkyl or C₆-i4-aryl, wherein

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are

Ci-io-alkyl or phenyl, or and R¹² together are

8. Compounds of formula

wherein

X is CI, Br or I, n is 0 or 1 , and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, CI, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(0)R²⁰³ and C(0)OR²⁰⁴, wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are Ci-₂₀-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C_2-2o-alkenyl, C_2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰¹⁰R²⁰¹¹, O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen, wherein R²⁰¹⁰, R^{201 1} , R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

with the proviso

that if n is 0 and X is CI, R¹ , R², R³ and R⁴ are not H, CI , CN , R²⁰⁰ or C(0)OR²⁰⁴, wherein R²⁰⁰ and R²⁰⁴ are Ci-20-alkyl,

that if n is 0 and X is Br, R¹ , R², R³ and R⁴ are not H, Br or R²⁰⁰,

wherein R²⁰⁰ is Ci-20-alkyl,

that if n is 1 and X is CI or Br, R¹ , R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are not H.

9. The compounds of claim 8, wherein n is 1.

10. The compounds of claim 9, wherein R¹ , R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same or different and are selected from the group consisting of F, CI , Br, I , CN , R²⁰⁰, OR²⁰¹ , SR²⁰², OC(0) R²⁰³ and C(0)OR²⁰⁴,

wherein R²⁰⁰, R²⁰¹ , R²⁰², R²⁰³ and R²⁰⁴ are Ci-₂₀-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C_2-2o-alkenyl, C_2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R^{201 1} , R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

The compounds of claim 10, wherein R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ the same or different and are selected from the group consisting of CI, Br, I , CN and

OR²⁰¹,

wherein R²⁰¹ is Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R²⁰¹⁰R^{201 1} , O-R²⁰¹², S-R²⁰¹³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{20 4}R²⁰¹⁵, O-R²⁰¹⁶, S-R²⁰¹⁷, N0₂, CN and halogen,

wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R³ and R⁵, respectively, R⁴ and R⁶ together are

12. Compounds of formula

wherein

n is 0 or 1 ,

R^{1 1} and R¹² are the same and are selected from the group consisting of CN , OR³⁰⁰,

Si(R³⁰¹)₃, N H R³⁰², N R³⁰³R³⁰⁴, SR³⁰⁵ and R³⁰⁶

wherein

R³⁰⁰, R³⁰¹ , R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵ and R³⁰⁶ are Ci-20-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl or wherein Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰⁰⁰R³⁰⁰¹ , O-R³⁰⁰² and S-R³⁰⁰³ and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl,

and R¹² together are selected from the group consisting of

wherein

L¹ and L² are Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene,

R²⁵ is H , Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl, Cs-s-cycloalkyl or C6-i4-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰¹⁰R^{301 1} , O-R³⁰¹² and S-R³⁰¹³, and

C6-i4-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R^{30 4}R³⁰¹⁵, O-R³⁰¹⁶ and S-R³⁰¹⁷,

wherein R³⁰¹⁰, R^{301 1} , R³⁰¹². R³⁰¹³, R³⁰¹⁴, R³⁰¹⁵, R³⁰¹⁶ and R³⁰¹⁷ are the same or different and are Ci-10-alkyl or phenyl,

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene, and

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, CI, Br, I , CN , R³¹⁰, OR^{31 1} , SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴, wherein R³¹⁰, R^{31 1} , R³¹², R³¹³ and R³¹⁴ are Ci-₂₀-alkyl, C₂-2o-alkenyl, C₂-2o-alkynyl,

Cs-s-cycloalkyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl, C2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen, wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

with the proviso that if

n is 0, R¹¹ and R¹² are both CN, then R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are not all H,

and that if

n is 1 , R¹¹ and R¹² are both CN or phenyl, and R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are H, then R¹⁷ and R²⁰ are not Br.

13. The compounds of any of claim 12, wherein R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

wherein

R³⁰⁰ and R³⁰¹ are Ci-20-alkyl, C2-2o-alkenyl, C2-2o-alkynyl or C6-i4-aryl,

wherein

Ci-2o-alkyl, C2-2o-alkenyl and C2-2o-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O-R³⁰⁰² and

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O-R³⁰⁰⁶ and S-R³⁰⁰⁷,

wherein R³⁰⁰⁰, R³⁰⁰¹ , R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹¹ and R¹² together are

wherein

L³ is a direct bond, Ci-6-alkylene, C6-i4-arylene, or Ci-6-alkylene-C6-i4-arylene-Ci-6-alkylene.

14. The compounds of claim 12 or 13, wherein R^{1 1} and R¹² together are

15. The compounds of any of claims 12 to 14, wherein n is 1.

The compounds of any of claim15, wherein

R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰, are the same or different and are selected from the group consisting of F, CI, Br, I , CN , R³¹⁰, OR^{31 1} , SR³¹², OC(0)R³¹³ and C(0)OR³¹⁴,

wherein R³¹⁰, R^{31 1} , R³¹², R³¹³ and R³¹⁴ are Ci-₂₀-alkyl, C₂-₂o-alkenyl, C₂-₂o-alkynyl,

C5-8-cycloalkyl or Ce-14-aryl,

wherein

Ci-2o-alkyl, C_2-2o-alkenyl, C_2-2o-alkynyl and Cs-s-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, N R³⁰²⁰R³⁰²¹ , O-R³⁰²², S-R³⁰²³, N0₂, CN and halogen,

Ce-14-aryl may be substituted with one or more substituents selected from the group consisting of Ci-10-alkyl, N R³⁰²⁴R³⁰²⁵, O-R³⁰²⁶, S-R³⁰²⁷, N0₂, CN and halogen, wherein R³⁰²⁰, R³⁰²¹ , R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are Ci-10-alkyl or phenyl, or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

17. Use of the compounds of formula (3) of any of claims 12 to 16 in electronic devices.

18. Use of the compounds of formula (3) of any of claims 12 to 16 as dye.